Process and catalyst for dehydrogenating primary alcohols to make carboxylic acid salts

ABSTRACT

This invention is directed to a process for making a salt of a carboxylic acid. The process comprises contacting a catalyst with an alkaline mixture comprising a primary alcohol. In one embodiment, the catalyst comprises a metal supporting structure (preferably a metal sponge supporting structure comprising at least about 10% by weight nickel) having a copper-containing active phase at the surface thereof and iron as a catalyst modifier. The supporting structure is resistant to deformation under the conditions of the dehydrogenation reaction. This invention is also directed to novel nickel-containing catalysts having a copper-containing active phase and iron as a catalyst modifier which may, for example, be used in the above process. This invention is further directed to processes for making such catalysts.

FIELD OF THE INVENTION

This invention generally relates to a novel process for making a carboxylic acid salt. More particularly, this invention relates to a process for dehydrogenating a primary alcohol (especially an amino alcohol, such as diethanolamine) to make a carboxylic acid salt (such as disodium iminodiacetic acid) using a copper-containing catalyst which also contains other metals that provide desirable characteristics, such as durability. This invention also generally relates to novel copper-containing catalysts that may be used in such a process, and to processes for making such catalysts.

BACKGROUND OF THE INVENTION

Carboxylic acid salts are useful in various applications. For example, salts of iminodiacetic acid may be phosphonomethylated to form N-(phosphonomethyl) iminodiacetic acid (“PMIDA”), which, in turn, may be oxidized to form N-(phosphonomethyl)glycine (known in the agricultural chemical industry as “glyphosate”). See, e.g., Gentilcore, U.S. Pat. No. 4,775,498 (disclosing a method to phosphonomethylate a salt of iminodiacetic acid); Ebner, et al., PCT/US99/03402 (disclosing a method for oxidizing PMIDA). Salts of nitrilotriacetic acid, for example, are excellent chelating agents, and consequently may be used as detergent builders, water-softening agents, scouring aids, dyeing assistants, paper-coating agents, scale inhibitors, and agents for preventing soap degeneration. And many carboxylic acid salts (e.g., salts of glycine, salts of iminodiacetic acid, etc.) may also be neutralized to their corresponding acids and then used, for example, as chelating agents; in food preparations; and as raw materials for making pharmaceuticals, agricultural chemicals, and pesticides. See, e.g., Franz, et al., Glyphosate: A Unique Global Herbicide (ACS Monograph 189, 1997) at pp. 234-41 (disclosing the use of glycine and iminodiacetic acid compounds as raw materials to form N-(phosphonomethyl) glycine).

It has long been known that a carboxylic acid salt may be prepared from a primary alcohol by dehydrogenating the alcohol using a copper-containing or silver-containing catalyst. In 1945, Chitwood first reported forming a carboxylic acid salt (specifically, the potassium salt of glycine) by oxidizing a primary alcohol (specifically, monoethanolamine) in an alkaline environment (specifically, in a mixture containing potassium hydroxide) using a copper-containing catalyst (specifically, copper metal or cupric oxide, which reportedly was reduced to copper metal under the reaction conditions) or a silver-containing catalyst (specifically, silver metal or silver oxide, which reportedly was reduced to silver metal under the reaction conditions). See Chitwood, U.S. Pat. No. 2,384,817. Chitwood, however, reported that copper-containing compounds are disadvantageous for this reaction because the copper coagulates over time, thereby causing the copper-containing compounds to have a short duration of maximum catalytic activity. Chitwood also reported that silver-containing compounds have relatively low activity (the silver oxide also reportedly coagulates over time).

In 1988, Goto et al. reported forming a carboxylic acid salt by oxidizing an ethanolamine compound in an alkaline solution (specifically, an aqueous solution containing the hydroxide of an alkali metal or an alkaline earth metal) using Raney copper. See Goto et al., U.S. Pat. No. 4,782,183. Goto et al. reported selectivities of at least 94.8% when dehydrogenating monoethanolamine, diethanolamine, and triethanolamine to form salts of glycine, iminodiacetic acid, and nitrilotriacetic acid, respectively. Raney copper, however, is disadvantageous because (like Chitwood's copper-containing compounds) Raney copper deactivates over time. See, e.g., Franczyk, U.S. Pat. No. 5,292,936, Table 1 (showing the reaction time for Raney copper to increase from 4 to 8 hours over 9 cycles).

Various developments have been reported which address the instability of copper-containing catalysts when used to dehydrogenate primary alcohols. Although these developments have made the use of copper catalysts more commercially viable, their results are still not entirely satisfactory.

Franczyk, for example, reports that copper-containing catalysts (particularly Raney copper) can be stabilized by using such a catalyst which also contains 50 to 10,000 parts per million of one or more various other metals selected from the group consisting of chromium, titanium, niobium, tantalum, zirconium, vanadium, molybdenum, tungsten, cobalt, nickel, bismuth, tin, antimony, lead, and germanium, with vanadium, chromium, and molybdenum being the more preferred metals. See Franczyk, U.S. Pat. Nos. 5,292,936; 5,367,112; and 5,739,390. Although such metals do tend to impart a stabilizing effect to a copper catalyst, this effect often decreases over time. See, e.g., Franczyk patents, Table 2 (showing the reaction time decreasing from 5.8 hours to 8.0 hours over 25 cycles) and Table 4 (showing the reaction time decreasing 3.1 to 5.5 hours over 12 cycles). This decrease is due, at least in part, to the fact that such metals tend to leach over time as the catalyst is used, particularly where the primary alcohol or the dehydrogenation product is a chelating agent (e.g., a salt of iminodiacetic acid).

Ebner et al. report using a catalyst comprising copper supported on an alkali-resistant support (particularly a carbon support) to dehydrogenate primary alcohols to make carboxylic acid salts. See Ebner et al., U.S. Pat. No. 5,627,125. This catalyst also comprises about 0.05 to about 10% by weight of a noble metal to anchor and disperse the copper to the support. Although Ebner et al. report shorter reaction times with their catalyst relative to previously disclosed copper-containing catalysts, their catalyst is costly due to the need for the noble metal to anchor the copper to the support. In addition, the added volume of Ebner et al.'s catalyst due to the carbon support can, in some instances, make handling the catalyst cumbersome, consequently reducing throughput. Further, Ebner et al.'s catalyst often loses activity over time with use (although the rate of deactivation is often less than the rate of deactivation of the Franczyk catalysts). See, e.g., Ebner et al., Table 1 (showing the reaction time increasing from 103 to 150 minutes over 9 cycles) and Table 2 (showing the reaction time increasing from 61 to 155 minutes over 8 cycles). As with the Franczyk catalysts, this problem tends to arise particularly where the primary alcohol or the dehydrogenation salt product is a chelating agent.

Other reported copper-containing catalysts contain a non-carbon support, such as, SiO₂, Al₂O₃, TiO₂, ZrO₂, and the like. See, e.g., Akzo Nobel, WO 98/13140 (disclosing a catalyst consisting of copper on ZrO₂). These supports, however, tend to be vulnerable to attrition under the reaction conditions normally present when dehydrogenating a primary alcohol, and are therefore usually less suitable than Ebner et al.'s carbon supports. This vulnerability to attrition tends to also cause these supports to exhibit poor filtration characteristics.

Use of copper-containing and silver-containing catalysts in other types of oxidation reactions has also been reported. Applicants, however, are unaware of any such disclosures which address the problems associated with copper-containing or silver-containing catalysts in processes involving the dehydrogenation of primary alcohols to form carboxylic acid salts.

Bournonville et al. report forming a ketone by dehydrogenating a secondary alcohol using a Raney nickel catalyst containing 0.1 to 10% by weight of copper, silver, gold, tin, lead, zinc, cadmium, indium, or germanium. See Boumonville et al., U.S. Pat. No. 4,380,673. This reaction, however, does not form a carboxylic acid salt—forming a carboxylic acid salt would further require the cleavage of an alkyl group from the carbonyl group and the subsequent attachment of a hydroxy salt to the carbonyl group. In addition, Bournonville et al. report that their reaction is catalyzed by the Raney nickel, and that the function of the additional metal (e.g., copper or silver) is to suppress hydrogenolysis side reactions. See Bournonville et al., col. 3, lines 45-47. This is in contrast to dehydrogenation reactions of primary alcohols using copper catalysts, such as Raney copper, where catalytic activity is provided primarily by copper atoms near the surface of the catalyst.

Yamachika et al. report forming benzaldehydes by reducing benzonitriles in the presence of acid and a Raney nickel catalyst which has been pre-treated with a copper salt solution. See Yamachika et al., U.S. Pat. No. 4,500,721. Yamachika et al. disclose that the conditions of catalyst pre-treatment should be sufficient to form a catalyst which contains 5 to 80% (more preferably 10 to 60%) by weight of copper. Yamachika et al. report that the presence of the copper increases the yield of benzaldehydes during the reaction. This reaction, however, is conducted in an acidic environment, is not directed to dehydrogenating primary alcohols (or any other alcohols), and does not form carboxylic acid salts.

Thus, although positive advances have been reported for converting a primary alcohol to a carboxylic acid salt using a copper-containing catalyst, there continues to be a need for a more economical liquid-phase process which uses a catalyst that has high surface area, has high activity, and exhibits stability (i.e., maintains its activity) over time with usage. This need particularly exists where the primary alcohol substrate and/or carboxylic acid salt product is a chelating agent (e.g., a salt of iminodiacetic acid).

The hydrogen produced by the dehydrogenation of primary alcohols can also be useful, particularly in the production of fuel cells. For example, W. H. Cheng, in Acc. Chem. Rev., vol. 32, 685-91(1999), describes the conversion of primary alcohols such as methanol to hydrogen as a safe and readily transportable source of hydrogen fuel cells for a variety of applications, most notably automotive applications. Thus, the more economical liquid-phase process of the present invention for the dehydrogenation of primary alcohols can also lead to more economical production of hydrogen from primary alcohols.

SUMMARY OF THE INVENTION

This invention provides, in part, for a novel and improved liquid-phase process for dehydrogenating primary alcohols to form salts of carboxylic acids, particularly such a process which uses a catalyst that maintains its activity, even in a mechanically-stirred, alkaline liquid containing one or more chelating agents; an improved process wherein an economically advantageous catalyst may be used (e.g., a catalyst that does not require the presence of expensive precious metals); an improved process which uses a catalyst that has a high surface area (e.g., at least about 20 m²/g, and more typically at least about 35 m²/g); an improved process which uses a copper-containing catalyst having less volume per unit surface area of copper than traditional catalysts containing copper supported on carbon; and an improved process wherein undesirable side reactions are reduced and selectivity for the desired carboxylic salt product is increased. Further, the present invention also provides for novel and improved copper-containing catalysts which may, for example, be used in liquid-phase oxidation reactions, particularly liquid-phase dehydrogenation reactions which convert primary alcohols to carboxylic acid salts; improved copper-containing catalysts that do not require the presence of expensive precious metals; improved copper-containing catalysts having a high surface area; improved copper-containing catalysts which maintain their activity with use over time, even in a mechanically-stirred, alkaline liquid containing one or more chelating agents; improved copper-containing catalysts having less volume per unit of copper surface area than the traditional catalysts comprising copper supported on carbon, thereby making them easier to filter; and improved copper-containing catalysts which have greater resistance to attrition than traditional catalysts comprising copper or comprising copper on a carbon support.

Briefly, therefore, the present invention is directed to a process for preparing a carboxylic acid salt by dehydrogenating a primary alcohol. The process comprises contacting an alkaline mixture comprising a primary alcohol with a dehydrogenation catalyst comprising a copper-containing active phase at the surface thereof, iron as a catalyst modifier and a supporting structure comprising nickel. In a preferred embodiment, the supporting structure of the catalyst comprises at least about 10% by weight nickel. In another preferred embodiment, the supporting structure of the catalyst comprises a metal sponge support comprising at least about 10% by weight nickel and from about 2% to about 30% by weight copper.

The present invention is further directed to a process for the preparation of a carboxylic acid salt by the dehydrogenation of a primary alcohol. The process comprises introducing a primary alcohol, a base, and a dehydrogenation catalyst into a reaction zone to form a dehydrogenation reaction mixture. A source of iron is then introduced into the dehydrogenation reaction mixture as a catalyst modifier. In a preferred embodiment, the dehydrogenation catalyst comprises a copper-containing active phase at the surface of a metal support wherein the metal support comprises at least about 10% by weight nickel.

The present invention is further directed to a process for making a salt of disodium iminodiacetic acid. The process comprises contacting a dehydrogenation catalyst with an aqueous mixture comprising an alkali metal hydroxide and diethanolamine. The catalyst comprises a copper-containing active phase and iron as a catalyst modifier at the surface of a metal support comprising at least about 50% nickel.

Still further, the present invention is directed to novel copper-containing oxidation catalysts. As used herein, the term “oxidation” includes, but is not limited to, dehydrogenation reactions. In one embodiment, the present invention is directed to a catalyst composition comprising a supporting structure having a copper-containing active phase and iron as a catalyst modifier at the surface thereof wherein the supporting structure comprises a metal and contains at least about 10% by weight nickel.

In another embodiment, the catalyst composition has a heterogeneous structure comprising a supporting structure, a surface active phase and an iron catalyst modifier wherein the supporting structure comprises a metal comprising at least about 10% by weight nickel, the surface active phase comprises at least about 50% by weight copper, and the iron catalyst modifier comprises from about 0.002% to about 5% by weight of the catalyst.

In another embodiment, the catalyst composition comprises a metal sponge support and the catalyst is characterized as being produced by a process comprising depositing a copper-containing active phase and an iron catalyst modifier on the surface of a metal sponge support containing at least about 60% by weight nickel and from about 2% to about 30% by weight copper.

Still further, the present invention is directed to a process for preparing an oxidation catalyst. The process comprises depositing a copper-containing active phase and an iron catalyst modifier onto the surface of a metal support comprising at least about 10% nickel and from about 2% to about 30% copper.

Other objects and features of this invention will be in part apparent and in part pointed out hereinafter.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The process of this invention may generally be used to convert any primary alcohol to a carboxylic acid salt. As used herein, a “primary alcohol” is any alcohol comprising a hydroxy group attached to a carbon which is bound to two hydrogen atoms, i.e., R—CH₂OH.

The process of the present invention dehydrogenates a primary alcohol to yield both a carboxylic acid salt and hydrogen gas. Typically, this reaction is carried out in a heated reaction zone containing the primary alcohol, a base, and a copper-containing or silver-containing catalyst. An example of this reaction is the dehydrogenation of monoethanolamine in a heated reaction zone containing KOH to form hydrogen gas and the potassium salt of glycine:

Another example of this reaction is the dehydrogenation of diethanolamine (sometimes described in the art as “DEA”) in a heated reaction zone containing NaOH to form hydrogen gas and disodium iminodiacetic acid (sometimes described in the art as “DSIDA”):

An additional example is the dehydrogenation of an N-alkyl-monoethanolamine to form a salt of an N-alkyl-glycine. The alkyl group could be, for example, methyl (—CH₃). In that instance, the dehydrogenation product would be a salt of N-methyl-glycine (i.e., a salt of sarcosine):

A further example is the dehydrogenation of triethanolamine to form a salt of nitrilotriacetic acid:

A. Preferred Primary Alcohol Substrate

The process of the present invention is particularly useful with primary alcohols which contain amino groups or other functionalities which are reactive and susceptible to side reactions. In particular, β-amino alcohols are susceptible to dehydrogenation of the C—N bond and subsequent dealkylation, consequently leading to the formation of typically undesirable side products.

In one embodiment of this invention, the primary alcohol is an alkanolamine (i.e., a compound wherein the nitrogen of an amine functionality is bonded directly to the carbon of an alkyl alcohol). In this embodiment, the primary alcohol is preferably a compound of the formula (I):

wherein n is an

-   -   integer ranging from 2 to 20; and R¹ and R² are independently         hydrogen, hydrocarbyl, or substituted hydrocarbyl.

A hydrocarbyl may be any group consisting exclusively of carbon and hydrogen. The hydrocarbyl may be branched or unbranched, may be saturated or unsaturated, and may comprise one or more rings. Suitable hydrocarbyl groups include alkyl, alkenyl, alkynyl, and aryl groups. They also include alkyl, alkenyl, alkynyl, and aryl groups substituted with other aliphatic or cyclic hydrocarbyl groups, such as alkaryl, alkenaryl, and alkynaryl.

A substituted hydrocarbyl may be any hydrocarbyl wherein at least one hydrogen atom has been substituted with an atom other than hydrogen or a group of atoms containing at least one atom other than hydrogen. For example, the hydrogen atom may be substituted with a halogen atom, such as a chlorine or fluorine atom. The hydrogen atom alternatively may be substituted with an oxygen atom or a group containing an oxygen atom to form, for example, a hydroxy group, an ether, an ester, an anhydride, an aldehyde, a ketone, or a carboxylic acid. The hydrogen atom also may be replaced with a group containing a nitrogen atom to form, for example, an amide or a nitro group. In addition, the hydrogen atom may be substituted with a group containing a sulfur atom to form, for example, —SO₃H.

Typically, R¹ and R² are independently either: hydrogen; —(CH₂)_(x)—(CH₃)_(m), x being an integer ranging from 0 to about 19 (particularly from 1 to 6, and even more particularly 1), m being either 1 or 2; —(CH₂)_(y)—OH, y being an integer ranging from 1 to about 20 (especially from 2 to 6); (CH₂)_(z)—COOH, z being an integer ranging from 1 to about 19 (especially from 1 to 5); or phosphonomethyl.

In some preferred embodiments, R¹ and R² are both hydrogen (i.e., the amine functionality shown in formula (1) is a primary amine). An example of such an alcohol is monoethanolamine.

In other preferred embodiments, R¹ is hydrogen and R² is hydrocarbyl or substituted hydrocarbyl (i.e., the amine functionality shown in formula (I) is a secondary amine). Examples of primary alcohols in which R² is hydrocarbyl include N-methylethanolamine, N-ethylethanolamine, N-isopropylethanolamine, N-butylethanolamine, and N-nonylethanolamine. Examples of primary alcohols in which R² is a substituted hydrocarbyl include primary alcohols wherein R² is —(CH₂)_(y)—OH and y is an integer ranging from 1 to about 20 (more preferably from 1 to 6). An example of such an alcohol is diethanolamine. Other examples of primary alcohols wherein R² is a substituted hydrocarbyl include N-(2-aminoethyl)ethanolamine, N-(3-aminopropyl)ethanolamine, N-(carboxymethyl)ethanolamine, and N-(phosphonomethyl)ethanolamine. N-substituted ethanolamines, for example, may be prepared using the various methods known in the art. For example, a ketone may be condensed with monoethanolamine in the presence of H₂, a solvent, and a noble metal catalyst. This reaction is described in, for example, Cope, A. C. and Hancock, E. M. J. Am. Chem. Soc., 64, 1503-6 (1942). N-substituted ethanolamines also may be prepared by combining a mono-substituted amine (such as methylamine) and ethylene oxide to form the mono-substituted ethanolamine. This reaction is described by, for example, Y. Yoshida in Japanese Patent Application No. 95-141575.

In yet other preferred embodiments, both R¹ and R² are independently hydrocarbyl or substituted hydrocarbyl (i.e., the amine functionality shown in formula (I) is a tertiary amine). Examples of primary alcohols in which R¹ and R² are independently hydrocarbyl include N,N-dimethylethanolamine, N,N-diethylethanolamine, and N,N-dibutylethanolamine. Examples of primary alcohols in which R¹ is hydrocarbyl and R² is substituted hydrocarbyl include primary alcohols wherein R² is —(CH₂)_(y)—OH and y is an integer ranging from 1 to about 20 (more preferably from 1 to 6). Such alcohols include, for example, N-methyldiethanolamine, N-ethyldiethanolamine, N-isopropyldiethanolamine, and N-butyldiethanolamine. Other examples of primary alcohols in which R¹ is hydrocarbyl and R² is substituted hydrocarbyl include N-ethyl,N-(2-aminoethyl)ethanolamine; N-ethyl,N-(2-aminoethyl)ethanolamine; and N-methyl,N-(3-aminopropyl)ethanolamine. Examples of primary alcohols in which R¹ and R² are independently substituted hydrocarbyl include primary alcohols wherein R¹ and R² are independently —(CH₂)_(y)—OH and y is an integer ranging from 1 to about 20 (more preferably from 1 to 6). An example of such an alcohol is triethanolamine. Other examples of primary alcohols in which R¹ and R² are independently substituted hydrocarbyl include tetra(2-hydroxyethyl)ethylenediamine and N-(phosphonomethyl),N-(carboxymethyl)ethanolamine.

B. Catalyst

It has been found in accordance with this invention that the softness of copper is at least one of the reasons that many traditional copper-containing catalysts (particularly copper sponge catalysts, such as those described by Goto et al. in U.S. Pat. No. 4,782,183) deactivate over time. More specifically, as such catalysts are used, their surfaces tend to deform and lose surface area and the catalyst particles themselves tend to agglomerate (this agglomeration, in turn, reduces access by the reactants to the catalyst's active sites). These effects are particularly pronounced when the traditional catalysts are used in a stirred-tank reactor (or otherwise subjected to mechanical agitation). Both the loss of surface area and the agglomeration of the catalyst particles reduce the surface area of the catalyst, thereby reducing activity of the catalyst. It has been discovered in accordance with this invention, however, that the rate of deactivation can be significantly reduced by combining the copper with at least one other metal which, at least in part, provides strengthening characteristics to the copper to make a more durable catalyst.

1. Catalysts Comprising Copper on a Metal Support

In one embodiment of this invention, the catalyst comprises a copper-containing active phase at the surface of an internal supporting structure. Preferably, the supporting structure is resistant to deformation under the conditions of the dehydrogenation reaction. The catalyst may comprise a homogeneous structure such as a monophasic alloy or a heterogenous structure having more than one discrete phase. Thus, the copper-containing active phase may be present at the surface of the supporting structure as a discrete phase such as a copper coating or an outer stratum; as a surface stratum, or as part of a homogeneous structure. It is important to note that in the case of a copper-containing active phase comprising an outer stratum of the catalyst, the internal supporting structure may be totally or partially covered by the copper-containing active phase.

Typically, the copper-containing active phase has a copper concentration of at least about 50% by weight copper, more preferably at least about 75% by weight copper, even more preferably at least about 90% by weight copper, and most preferably at least about 95% by weight copper. When the copper-containing active phase is present as a surface stratum, outer stratum or as a discrete phase or coating, the surface of the support preferably comprises from about 0.005 to about 0.5 grams (more preferably from about 0.03 to about 0.5 grams, even more preferably from about 0.08 to about 0.35 grams) of copper per gram of said metal support. In other words, the catalyst preferably contains copper deposited at the surface of the metal support in a concentration ranging from about 0.005 to about 0.5 grams (more preferably from about 0.03 to about 0.5 grams, even more preferably from about 0.08 to about 0.35 grams) of copper for every gram of metal support.

a. Supporting Structure

The supporting structure may comprise any material suitable for supporting a copper-containing active phase, preferably any non-brittle material having a tensile strength and/or yield strength greater than copper. Typically the supporting structure comprises a metal support. Suitable metal supports may comprise a wide variety of compositions. In general, however, at least about 10% by weight of the metal support is non-copper metal. In one particularly preferred embodiment, at least about 50% (more preferably at least about 65%, about 80%, about 85% or even at least about 90%) by weight of the metal support is non-copper metal (this non-copper metal may comprise a single metal or multiple metals). Alternatively, in another particularly preferred embodiment, at least about 50% (more preferably from about 60% to about 80%) by weight of the metal support is copper.

The metal or alloy from which the metal support is made preferably has a tensile strength and/or yield strength which is greater than copper alone. It is particularly preferred for the composition to have a yield strength of greater than about 70 Mpa, more preferably greater than 100 Mpa, and even more preferably at least 110 Mpa. It is also particularly preferred for the composition to have a tensile strength of greater than 221 Mpa, more preferably greater than 275 Mpa, and even more preferably greater than 300 Mpa. For example, a composition containing 70% by weight copper and 30% by weight zinc reportedly has a yield strength of 124 Mpa and a tensile strength of 331 Mpa; a composition containing 90% by weight copper and 10% by weight nickel reportedly has a yield strength of 110 Mpa and a tensile strength of 303 Mpa; and a composition containing 70% by weight copper and 30% by weight nickel reportedly has a yield strength of 138 Mpa and a tensile strength of 372 Mpa. See A. S. Krisher and O. W. Siebert in Perry's Chemical Engineers' Handbook, pp. 23-42 to 23-49 (6th ed., R. H. Perry, D. Green, and J. O. Maloney, eds, McGraw Hill, New York, N.Y. 1984).

In many instances, it is preferred for the non-copper metal in the support to be relatively non-reactive in the alkaline (and often chelating) environments of this process. Such metals include, for example, nickel, gold, palladium, and platinum. Of these metals, nickel is typically the more preferred because, for example: (1) nickel generally costs less than the other metals, and (2) depositing copper onto a nickel-containing support is typically less difficult relative to depositing copper onto a support containing a significant amount of the other listed metals. For example, copper may be deposited onto a nickel-containing support using the simple process of electrochemical displacement deposition. There are, however, other techniques (e.g., electroless plating and metal-organic chemical vapor deposition) which may often be used to deposit copper onto supports comprising gold, palladium, and/or platinum.

It should be recognized that, other metals (e.g., zinc, cobalt, iron, and tin) which show some reactivity in alkaline and/or chelating environments also may often be suitable for supporting the copper-containing active phase within the present invention. This is particularly true because the copper at the surface of the metal support tends to act as a shield to protect the metal in the support from the reaction environment. It is also particularly true where a less-alkaline-resistant metal may provide an advantage over a more-alkaline-resistant metal. For example, it is often desirable to deposit copper onto the surface of the metal support using electrochemical displacement deposition (also described in the art as “immersion plating”). In that instance, the metal support preferably contains metal which has a reduction potential to the metal which is less than the reduction potential to the metal of copper, i.e., a reduction potential to the metal of less than about +343 mVolts vs. NHE (normal hydrogen electrode). Metals having such a reduction potential include, for example, nickel, zinc, tin, iron, and cobalt. The presence of such a metal near the surface of the support allows for simple deposition of copper metal at the surface of the support by contacting the surface with a copper salt (normally a Cu(II) salt) solution. More specifically, during displacement deposition, such a metal near the surface of the support tends to oxidize (and go into solution as an ion) when contacted with a copper ion solution. As this occurs, the copper ions in solution near the support surface are reduced to copper metal, which, in turn, deposits on the surface of the support. The reaction which occurs, for example, when a support comprising nickel is contacted with a copper salt solution is: Cu²⁺+Ni⁰→Cu⁰+Ni²⁺

As the foregoing suggests, when the catalyst is prepared by depositing copper onto the surface of the support using displacement deposition, it is particularly preferable to use a nickel-containing support because nickel has at least three desirable characteristics: (1) a reduction potential to the metal which is less than the reduction potential to the metal of copper, (2) relative stability in the reaction conditions of this invention, and (3) greater mechanical strength and resistance to attrition than copper.

However, it is important to note that, when the catalyst is prepared by depositing copper onto the surface of a nickel support, it may be preferable to further include iron as a catalyst modifier. For example, it is generally known that copper-nickel catalysts can be effective in catalyzing the elimination of one carbon from an alcohol to produce an alkane or alkene and a byproduct containing one carbon, typically carbon monoxide. The reaction, which is described by A. Baiker and W. Richarz in Helv. Chim. Acta 60, 2958-63 (1977) is catalyzed by nickel and is generally undesired within the process of the present invention. Thus, it has been found that the use of iron as a catalyst modifier within the process of the present invention can reduce the activity of exposed nickel to suppress the occurrence of one carbon elimination reactions, thereby increasing selectivity of the catalyst for the desired carboxylic acid salt.

Likewise, the presence of iron as a catalyst modifier may also be preferable when the process of the present invention is used to dehydrogenate diethanolamine using a copper on nickel catalyst. For example, exposed nickel in the reaction mixture for dehydrogenating diethanolamine tends to catalyze the formation of byproducts (e.g., sodium sarcosinate), thus reducing selectivity for the desired iminodiacetic acid salt (e.g., disodium iminodiacetate). However, without being held to a particular theory, it has been found that using iron as a catalyst modifier with a copper on nickel catalyst for the dehydrogenation of diethanolamine can reduce the activity of the exposed nickel to partially suppress the formation of byproducts, particularly sarcosine, and increase selectivity of the catalyst for producing disodium iminodiacetate.

When the metal support comprises more than one metal, it is preferred that at least about 80% by weight (more preferably at least about 85% by weight, even more preferably at least about 90% by weight, and still even more preferably essentially all) of the metals in the support are in the form of an alloy. In a particularly preferred embodiment, the metals form a substitutional alloy (also known as a “monophasic alloy”), wherein the alloy has a single, continuous phase. Although multiphasic alloys (i.e., alloys comprising at least 2 discrete phases) may be used, monophasic alloys are generally preferred because it is difficult to evenly distribute copper onto a multiphasic support surface because copper tends to preferentially coat the copper-rich portions relative to the copper-poor portions of the surface. Whether the alloy is monophasic or multiphasic will depend on the components of the alloy and their concentrations. Typically, for example, metal supports consisting essentially of nickel and copper are monophasic at any nickel concentration. But when, for example, the support consists essentially of copper and zinc, there are many zinc concentrations (typically, concentrations greater than about 35% by weight) which lead to the alloy being bi-phasic.

It should be recognized that the support may also comprise non-metal atoms (e.g., boron, carbon, silicon, nitrogen, phosphorus, etc.) in addition to the metal atoms. An alloy containing such non-metal is typically described in the art as an “interstitial alloy.” Supports comprising such an alloy may have various advantages, such as enhanced mechanical strength. Typically, however, catalysts comprising an interstitial alloy contain at least about 70% metal.

In a particularly preferred embodiment, the metal support is a metal sponge. As used herein, the term “metal sponge” refers to a finely divided and porous form of metal having a surface area of at least about 20 m²/g, and more typically at least about 35 m²/g. Such surface area may be measured using, for example, the B.E.T. (Brunauer/Emmett/Teller) method which is well known in the art. It has been found in accordance with this invention that if copper is coated onto the surface of a metal sponge support, the resulting material exhibits the mechanical strength and high surface area of the sponge support combined with the desired catalytic activity of the copper.

Metal sponges are available from W.R. Grace & Co. under the trademark “Raney” and are often generally described in the art as “Raney metals,” irrespective of source. Applicants use the term “metal sponge” rather than “Raney metal” to ensure that the claims appended hereto are not limited to the use of W.R. Grace & Co.'s metal sponges.

Typically, the preferred average particle size of the metal sponge is at least about 0.1 μm, preferably from about 0.5 to about 100 μm, more preferably from about 15 to about 100 μm, even more preferably from about 15 to about 75 μm, and still even more preferably from about 20 to about 65 μm.

Sponge supports can be prepared by techniques generally known to those skilled in the art. See, generally, E. Lieber and F. L. Morritz, Adv. Catal., 5, 417 (1953) (a general review directed to sponge metals). In general, techniques for making metal sponges comprise forming an alloy which contains about 50% by weight of a leachable metal (typically aluminum) and about 50% by weight of the desired metal(s); grinding the alloy to a desired particle size; and treating the alloy particles with an aqueous solution of an alkali metal hydroxide (preferably NaOH) to leach at least a portion of the leachable metal from the alloy. It is often preferred to conduct the leaching at a temperature of less than about 50° C. (more preferably no greater than about 40° C., and even more preferably from about 20° to about 40° C.). As the leachable metal leaches from the particle, it leaves behind voids (e.g., pores) which dramatically increase the surface area of the particle.

It should be recognized that the above-described technique is not the only method for making sponge metals. An iron sponge, for example, may be formed by reducing iron oxide at such low temperatures that melting does not occur, typically by mixing iron oxide and coke and applying a limited increase in temperature. See Hawley's Condensed Chemical Dictionary, 13th Ed., p. 621 (Rev. by Richard J. Lewis, Sr., Van Nostrand Reinhold, New York, N.Y. 1997).

References describing the preparation of nickel sponges include, for example, Augustine, Robert L., Catalytic Hydrogenation Techniques and Applications in Organic Synthesis (Marcel Dekker, Inc., 1965), appendix at pp. 147-149. See also, Hawley's Condensed Chemical Dictionary, 13th Ed., p. 955 (Rev. by Richard J. Lewis, Sr., Van Nostrand Reinhold, New York, N.Y. 1997) (describing the generally recognized technique of making sponge nickel by leaching aluminum from an alloy containing 50% by weight nickel and 50% by weight aluminum using a 25% by weight caustic soda solution).

References describing the preparation of nickel/copper sponges include, for example, D. J. Young, M. S. Wainwright, and R. B. Anderson, J. Catal., 64, 116 (1980). Such references also include, for example, M. S. Wainwright and R. B. Anderson, J. Catal., 64, 124 (1980).

References describing the preparation of copper/zinc sponges include, for example, A. J. Bridgewater, M. S. Wainwright, D. J. Young, and J. P. Orchard, Appl. Catal., 7, 369 (1983). Such references also include, for example, M. S. Wainwright, “Raney Copper and Raney Copper-Zinc Catalysts,” Chem. Ind. (Dekker), 68, 213-30 (1996).

References describing the preparation of nickel/iron sponges include, for example, H. J. Becker and W. Schmidt in “Raney nickel-iron catalyst,” Ger. Offen. DE 2713374 19780928 (1978).

References describing the preparation of nickel/cobalt sponges include, for example, J. P. Orchard, A. D. Tomsett, M. S. Wainwright, and D. J. Young in “Preparation and Properties of Raney Nickel-Cobalt Catalysts,” J. Catal., vol. 84, pp. 189-99 (1983).

Various metal sponges are also commercially available from, for example, W.R. Grace & Co. (Davison Division, Chattanooga, Tenn.); Gorwara Chemical Industries (Udaipur, India); Activated Metals & Chemicals, Inc. (Sevierville, Tenn.); Degussa-Huls Corp. (Ridgefield Park, N.J.); Engelhard Corp. (Iselin, N.J.); and Aldrich Chemical Co. (Milwaukee, Wis.).

Examples of suitable commercially-available nickel sponges, for example, include Raney® 2800 (characterized by the manufacturer as having at least 89 wt. % Ni; no greater than 9.5 wt. % Al; no greater than 0.8 wt. % Fe; an average particle size in the range of 20-60 μm; a specific gravity of approximately 7; and a bulk density of 15-17 lbs/gal based on a catalyst slurry weight of 56% solids in water), Raney® 4200 (characterized by the manufacturer as having at least 93 wt. % Ni; no greater than 6.5 wt. % Al; no greater than 0.8 wt. % Fe; an average particle size in the range of 20-50 μm; a specific gravity of approximately 7; and a bulk density of 15-17 lbs/gal based on a catalyst slurry weight of 56% solids in water), Raney® 4310 (characterized by the manufacturer as having at least 90 wt. % Ni; no greater than 8 wt. % Al; 0.5-2.5 wt. % Mo; no greater than 0.8 wt. % Fe; an average particle size in the range of 20-50 μm; a specific gravity of approximately 7; and a bulk density of 15-17 lbs/gal based on a catalyst slurry weight of 56% solids in water), Raney® 3110 (characterized by the manufacturer as having at least 90 wt. % Ni; 0.5-1.5 wt. % Mo; no greater than 8.0 wt. % Al; no greater than 0.8 wt. % Fe; an average particle size in the range of 25-65 μm; a specific gravity of approximately 7; and a bulk density of 15-17 lbs/gal based on a catalyst slurry weight of 56% solids in water), Raney® 3201 (characterized by the manufacturer as having at least 92 wt. % Ni; no greater than 6 wt. % Al; no greater than 0.8 wt. % Fe; 0.5-1.5 wt. % Mo; an average particle size in the range of 20-55 μm; a specific gravity of approximately 7; and a bulk density of 15-17 lbs/gal based on a catalyst slurry weight of 56% solids in water), Raney® 3300 (characterized in U.S. Pat. No. 5,922,921 as having 90-99.1 wt. % Ni; no greater than 8.0 wt. % Al; no greater than 0.8 wt. % Fe; 0.5-1.5 wt. % Mo; no greater than 0.8 wt. % Ni; an average particle size in the range of 25-65 μm; a specific gravity of approximately 7; and a bulk density of 15-17 lbs/gal based on a catalyst slurry weight of 56% solids in water), Raney® 2724 (Cr-promoted), and Raney® 2724 (Cr-promoted), all sold by W.R. Grace & Co.; the catalyst described as “Raney nickel” sold by Gorwara Chemical Industries; A-4000 and A-5000, sold by Activated Metals & Chemicals, Inc.; nickel ABMC, sold by Degussa-Huls Corp.; and “Raney nickel,” Catalog No. 22, 167-8, sold by Aldrich Chemical Co.

Examples of suitable commercially-available cobalt sponges include Raney® 2700 (characterized in U.S. Pat. No. 5,922,921 as having 93.0 wt. % Co; no greater than 6.0 wt. % Al; no greater than 0.7 wt. % Fe; no greater than 0.8 wt. % Ni; an average particle size in the range of 20-50 μm; a specific gravity of approximately 7; and a bulk density of 15-17 lbs/gal based on a catalyst slurry weight of 56% solids in water), sold by W.R. Grace & Co.; the cobalt sponge catalysts reportedly manufactured by the Raney process and sold by Activated Metals & Chemicals, Inc.; and cobalt ABMC, sold by Degussa-Huls Corp.

b. Deposition of the Copper-Containing Active Phase

The copper-containing active phase may be deposited at the surface of a metal support using various techniques well-known in the art for depositing metal onto metal surfaces. These techniques include, for example, liquid phase methods, such as electrochemical displacement deposition and electroless plating; and vapor phase methods such as physical deposition and chemical deposition. The following discussion will focus on the two particularly preferred techniques of electrochemical displacement deposition and electroless plating. This preference stems from the fact that the other techniques are generally more complicated and/or more costly.

It is important to note that copper is at least partially miscible with most support metals of interest and is completely miscible with nickel. Thus, it has been found that the copper deposition process may result in the catalyst having copper, or more particularly a copper-containing active phase, at the surface of the support as part of a discrete phase such as an outer stratum or coating, at the surface of the support as part of a surface stratum, or the copper may migrate from the surface of the support into the bulk of the support. Without being held to a particular theory, it is believed that the catalyst surface can move, sinter or otherwise restructure during the reaction conditions of the deposition process resulting in such variations of form in the copper-containing active phase. Nonetheless, it has been found that the copper deposition process results in an overall increase in the copper content of the catalyst with the deposited copper predominantly present at or near the surface of the catalyst, which is richer in copper than before deposition.

i. Electrochemical Displacement Deposition of Copper

Copper may be deposited onto the surface of the supporting structure via electrochemical displacement deposition wherein copper ions in a copper-salt solution in contact with the support are reduced to copper metal as non-copper metal near the surface of the support is oxidized. The copper metal, in turn, forms a coating on the surface of the support, while the non-copper ions go into solution. A general discussion related to electrochemical displacement deposition may be found in, for example, G. A. Krulik and N. V. Mandich, “Metallic Coatings (Survey)”, Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed. (J. I. Kroschwitz and M. Howe-Grant, eds., Wiley, New York, N.Y., 1995) Vol. 16, pp. 258-91.

Without providing an exhaustive list, suitable copper salts for displacement deposition include, for example, the nitrate, sulfate, chloride, and acetate salts of copper. Salts containing copper in the divalent state (i.e., Cu(II)) are typically the most preferred. Although salts containing monovalent and trivalent copper may be used, they are typically less preferred because they tend to be unstable, commercially less available, and/or insoluble in the alkaline mixture.

Before and during the displacement deposition, the metal support preferably is protected from air by, for example, keeping it immersed in water, maintaining it under a non-oxidizing atmosphere (noble gas or N₂, preferably N₂), and/or sparging a suspension containing the support with a non-oxidizing gas. In one particularly preferred embodiment, the metal support surface is reduced before the displacement deposition. The surface may be reduced, for example, by contacting the support with a solution of sodium borohydride (NaBH₄), formaldehyde, or other reducing agent; or by contacting the support with H₂ or another reducing gas at an elevated temperature. Example 5 demonstrates such a technique.

To initiate the displacement deposition, the copper salt may be added as a dry powder to a solution containing the metal support, but more preferably is added as an aqueous solution. While adding the copper salt, the solution containing the metal support preferably is gently stirred at a rate sufficient to keep the support particles suspended. Although the copper salt may be added all at once, the salt is preferably added slowly so that the salt concentration does not exceed the concentration at which the salt begins to precipitate. Typically, the salt is added over a period of at least about 30 minutes, but no greater than about 2 hours (such slow salt addition is often unnecessary in the presence of a strong chelating agent, such as ethylenediaminetetraacetic acid, which keeps the copper salt solubilized). After the salt has been added, the resulting mixture preferably is stirred for at least about 15 minutes. Afterward, the stirring may be discontinued so that the catalyst can settle to allow the supernatant to be removed by decantation or other means. The catalyst may then be re-suspended in the desired solvent for introduction into the dehydrogenation reaction zone.

During the displacement deposition, the pH of the solution containing the metal support preferably is adjusted so that the displaced metal will tend to remain soluble and not redeposit onto the support. Metal ions are generally more soluble under acidic conditions than basic conditions (with the exception of alkali metal ions, which are generally soluble under both acidic and basic conditions). Thus, the pH is preferably low enough to ensure that the displaced metal remains in solution and does not redeposit onto the catalyst as, for example, an oxide or hydroxide.

If, during the displacement deposition, the copper is deposited at a rate which tends to unevenly coat the support, a more even coating may often be obtained by including a protecting chelating agent in the copper salt solution to control (i.e., slow) the rate of copper deposition so that a more even coat may be obtained. A chelating agent may also be beneficial to inhibit the displaced metal from redepositing onto the metal support. Suitable chelating agents include, for example, hydroxy carboxylic acids (e.g., lactic acid, malic acid, citric acid, and tartaric acid) and salts thereof (e.g., sodium potassium tartrate, also described in the art as “Rochelle salt”), with tartaric acid and salts thereof being preferred. Chelators which contain amines (e.g., salts of iminodiacetic acid, nitrilotriacetic acid, and particularly ethylenediaminetetraacetic acid (also known as “EDTA”)) are particularly preferred, for example, for depositing copper on metal supports comprising nickel. Normally, at least one molar equivalent (based on moles of copper ions) of chelating agent is preferably included. Even more preferably, from about 1.2 to about 3.0 (still even more preferably from about 1.2 to about 1.8) molar equivalents of chelating agent are included in the mixture. Although concentrations of greater than 3.0 molar equivalents may be used, such additional concentrations usually do not provide any greater benefits. Concentrations of greater than 3.0 molar equivalents also tend to cause the chelating agent to precipitate and may create greater burdens downstream during product purification.

Examples 1, 3, 5, and 7 illustrate electrochemical displacement deposition of copper onto a metal sponge support. The same examples also illustrate the use of a chelating agent during such a deposition.

In a particularly preferred method for the deposition of copper onto a metal support, electrochemical displacement deposition is conducted under basic conditions followed by electrochemical displacement deposition under acidic conditions. Preferably, the metal support is free of surface oxidation at the time of the plating. However, in instances where the metal support has an oxidized surface (i.e., when the support has been exposed to air (even while under water) for 6 or more months), it is particularly preferable to pre-treat the support with a reducing agent. For example, the support may be stirred in a sodium borohydride solution, which preferably comprises a solution having a pH of at least about 10 and at least about 1 gram of sodium borohydride per 25 grams of metal support. Generally, contacting the support with the reducing agent for about 5 minutes to about 2 hours at room temperature is sufficient.

To begin the electrochemical displacement deposition, the catalyst support is slurried into a water or alcohol solution, preferably in water, and the pH is adjusted to 7. A copper salt as described above is added to the metal support slurry, preferably as a solution comprising the copper salt and a chelator, particularly an amine chelator such as EDTA. Preferably, the copper salt solution contains about 10% to about 30% copper by weight with respect to the metal support. A solution of an alkali metal hydroxide (such as NaOH) or another suitable base is then slowly added to the slurry, preferably with continuous stirring and nitrogen sparging. The alkali metal hydroxide solution preferably contains at least one equivalent of alkali metal hydroxide with respect to the copper salt, and more preferably three equivalents of alkali metal hydroxide with respect to the copper salt. Although this step comprises a displacement deposition reaction, a majority of the oxidized metal from the support remains closely associated with the support and is removed in the subsequent acidic step. Moreover, the first, basic displacement deposition reaction results in the deposition of cuprous oxide as well as metallic copper at the surface of the support.

After the basic displacement deposition, the supernatant is removed by decanting or other means and copper is further deposited onto the surface of the catalyst support under acidic conditions. After decantation, the metal support is again slurried into an alcohol or water solution. An acid buffer solution, preferably a gluconic acid/gluconate buffer, is added to the metal support slurry to reduce the pH to below about 4. The temperature of the buffer is preferably between about 40° C. and about 90° C. The acid buffer may comprise any suitable chelator which is capable of controlling residual metals in solution while subsequently lowering pH. For example, gluconic acid is preferred for depositing copper onto the surface of metal supports comprising nickel because gluconic acid is a good chelator for residual aluminum ions present in solution. A copper salt as described above is then added to the metal support slurry, preferably as a copper salt solution, over a period of about 5 to about 40 minutes with continuous stirring and nitrogen sparging. Afterward, the stirring may be discontinued so that the catalyst can settle to allow the supernatant to be removed by decantation or other means. The catalyst may then be re-suspended in the desired solvent for introduction into the dehydrogenation reaction zone.

ii. Electroless Plating of Copper

Electroless plating may alternatively be used to deposit copper onto the surface of the support. Like displacement deposition, electroless plating comprises reducing copper ions to copper metal in a solution in contact with the support. However, unlike displacement deposition, substantially all the copper ions are reduced by an external reducing agent rather than the support itself. As the reducing agent reduces the copper ions in the solution to copper metal, the copper metal forms a coating on the surface of the support. It is generally preferred for electrochemical displacement plating to be suppressed during electroless plating. This is preferably accomplished by the presence of chelators, such as the amine chelators discussed above (particularly salts of EDTA). The chelator is preferably added to the copper ion solution before contacting the metal support to avoid electrochemical displacement deposition from occurring in the absence of the reducing agent.

Suitable sources of copper ion for use in electroless plating include copper salts including, for example, the nitrate, sulfate, chloride, acetate, oxalate, and formate salts of copper. Salts containing copper in the divalent state (i.e., Cu(II)) are typically the most preferred. Although salts containing monovalent and trivalent copper may be used, they are typically less preferred because they tend to be unstable, commercially less available, and/or insoluble in the alkaline mixture. Other sources may include copper complexes such as copper decanoates, copper naphthanates and copper acetylacetonate.

The copper ion solution may be aqueous or non-aqueous. Suitable non-aqueous solvents generally include alcohols, liquid aromatic hydrocarbons such as benzene and toluene, mineral spirits and THF.

A wide variety of suitable reducing agents may be used. These include, for example, sodium hypophosphite (NaH₂PO₂), formaldehyde (CH₂O) and other aldehydes, formic acid (HCOOH), salts of formic acid, salts of borohydride (e.g., sodium borohydride (NaBH₄), salts of substituted borohydrides (e.g., sodium triacetoxyborohydride (Na(CH₃CO₂)₃BH), sodium alkoxides, and hydrazine (H₂NNH₂). Sodium borohydride is a particularly preferred reducing agent in aqueous electroless plating methods because it is readily available, may be solubilized without heating, and has sufficient activity at room temperature to enable plating to be completed within about 1 hour. For platings in non-aqueous copper ion solutions, the preferred reducing agent is gaseous hydrogen owing to the good solubility of hydrogen in organic solvents.

In an aqueous electroless plating method, the reducing agent is typically added slowly (preferably over a period of from about 5 minutes to 3 hours, and more preferably from about 15 minutes to about 1 hour) to a slurry of the metal support in water or an alcohol under an inert atmosphere (e.g., N₂). If the reducing agent is instead first added to the copper salt, it is preferably added to a solution which contains the copper salt and also a chelator (the presence of the chelator inhibits the reduction of the copper ions before the copper-salt solution is combined with the metal support).

The metal support preferably is essentially free of surface oxidation at the time of the plating. Consequently, in instances where the metal support has an oxidized surface (such as when the support has been exposed to air (even while under water) for 6 or more months), it is particularly preferable to pre-treat the support with a reducing agent. For example, the support may be stirred in a sodium borohydride solution, which preferably comprises a solution having a pH of at least about 10 and at least about 1 gram of sodium borohydride per 25 grams of metal support. Contacting the support with the reducing agent for about 5 minutes to about 2 hours at room temperature is generally sufficient to remove surface oxidation.

Examples 9, 11, 13 and 23 illustrate the use of electroless plating to deposit copper onto the surface of a metal support.

iii. Use of an Iron Catalyst Modifier

As described above, it is sometimes preferable to use iron as a catalyst modifier when using a copper/nickel catalyst within the process of the present invention. For example, it has been found that iron as a catalyst modifier is useful to reduce the activity of exposed nickel in the reaction mixture for catalyzing one carbon elimination reactions, or in the case of dehydrogenating diethanolamine, to reduce the activity of exposed nickel for catalyzing the formation of byproducts. By reducing the activity of nickel for catalyzing such unwanted side reactions within the process of the present invention, the presence of an iron catalyst modifier can increase selectivity for the desired carboxylic acid salt.

The amount of iron to be used as a catalyst modifier can vary within wide limits; and, experience to date does not suggest that a particular amount of iron catalyst modifier is critical or limiting for reducing the activity of exposed nickel within the process of the present invention. Typically, the total concentration of iron as a catalyst modifier is from about 0.002% to about 5% by weight of the catalyst, preferably from about 0.002% to about 2.5% by weight of the catalyst, more preferably from about 0.05% to about 3% by weight of the catalyst, and even more preferably from about 0.5% to about 1.5% by weight of the catalyst. Although concentrations of iron greater than about 5% by weight of the catalyst can be used, exceeding such a concentration does not generally show any additional benefits in reducing the activity of exposed nickel in the reaction mixture and may reduce the activity of the catalyst in the dehydrogenation reaction.

Like the catalyst active phase, the iron catalyst modifier can be present at the surface of the supporting structure as part of a discrete phase such as a coating or stratum or an outer stratum; as a surface stratum, or as part of a homogeneous structure. Preferably, the iron catalyst modifier is added to the surface of the catalyst simultaneously with or immediately following the deposition of copper. For example, when copper is deposited on the surface of the catalyst support using electrochemical displacement deposition or electroless plating as described above, it is important to deposit the iron after the deposition of copper because the iron will dissolve under acidic plating conditions. As demonstrated in Example 28, a preferred method for depositing iron as a catalyst modifier at the surface of the catalyst comprises slowly raising the pH of a solution of cupric ion and iron, preferably iron in the divalent state (i.e., Fe(II)), in the presence of a chelator discussed above such as an amine chelator (e.g., salts of EDTA). Alternatively, iron can typically be added to the catalyst of the present invention by simply contacting the catalyst with an aqueous solution containing a salt of iron. For example, it has been found that iron can function as a catalyst modifier simply by adding a source of iron directly to the dehydrogenation reaction mixture. Suitable sources of iron include powders of iron and carbon steel, powders of iron oxides (preferably magnetite, i.e., Fe₃O₄) or soluble sources of iron such as Na₂(FeO₄) in concentrated sodium hydroxide. Further, it is believed that iron may also be incorporated into the alloy-metal support as a catalyst modifier prior to activation, for example, by leaching of an iron-copper-nickel-aluminum alloy as described above for the preparation of a metal sponge support. However, this method is less preferred as it has been found that much of the iron introduced to the alloy dissolves during electrochemical displacement deposition or electroless plating.

Examples 28 demonstrates the deposition of iron as a catalyst modifier after the electrochemical displacement deposition of copper onto a nickel sponge support and Example 29 demonstrates the use of an iron modified catalyst in the dehydrogenation of diethanolamine.

2. Other Copper-Containing Catalysts

In another embodiment of this invention, the catalyst does not comprise copper coated on a metal support (i.e., there is no discrete copper deposited on or coating the surface of the catalyst). Rather, the copper is mixed (preferably in the form of an alloy) with other metals which provide desirable properties to provide a catalyst active phase. In this embodiment, from about 10% to about 85% (more preferably from about 50% to about 85%, even more preferably from about 60% to about 80%, and still more preferably from about 60% to about 75%) by weight of the catalyst is copper. Preferably, the catalyst is in the form of a metal sponge. In a particularly preferred embodiment, the catalyst comprises greater than about 1% by weight nickel, tin, or a combination thereof. In another particularly preferred embodiment, the catalyst comprises less than about 1% by weight metal oxide.

It should be recognized that this embodiment is less preferred if there are significant adverse effects from the non-copper metal of the catalyst being in contact with the other components in the reaction zone. For example, a catalyst having a copper coating is more preferred if the catalyst contains a metal which catalyzes an undesirable side reaction that reduces the conversion of the primary alcohol and/or selectivity for the desired carboxylic acid salt. This occurs, for example, where a catalyst containing nickel is used to dehydrogenate diethanolamine to form a salt of iminodiacetic acid. Without a copper coating, the exposed nickel tends to catalyze the formation of a glycine salt byproduct, thus reducing selectivity for the desired iminodiacetic acid salt. By using a copper coating or an iron catalyst modifier as described above, however, the activity of the nickel can often be minimized.

A copper coating is also preferred if, for example, a non-copper metal in the catalyst is vulnerable to attack under the reaction conditions to an extent which may significantly reduce the life of the catalyst. Metals which are often vulnerable to such attack under alkaline or chelating reaction conditions include zinc, tin, cobalt, and iron.

3. Optional Supplemental Metal

The catalyst may optionally contain one or more supplemental metals selected; from the group consisting of chromium, titanium, niobium, tantalum, zirconium, vanadium, molybdenum, manganese, tungsten, cobalt, nickel, bismuth, tin, antimony, lead, and germanium. The presence of such a metal(s) tends to extend the life of the catalyst, i.e., increase the number of reaction runs in which the catalyst can be used before its activity decreases to unacceptable levels. Of the above elements, vanadium, chromium, molybdenum, and combinations thereof (especially chromium and molybdenum) are particularly preferred.

The amount of the supplemental metal(s) can vary within wide limits. Preferably, the total concentration of supplemental metals is at least about 10 parts per million parts of copper in the catalyst by weight. More preferably, the total concentration of the supplemental metals in the catalyst is from about 0.002% to about 5% by weight, more preferably from about 0.002% to about 2.5% by weight, even more preferably from about 0.005% to about 2% by weight, and still even more preferably from about 0.5% to about 1.5% by weight. Typically, the total concentration of supplemental metals does not exceed about 5% by weight. Although greater concentrations of supplemental metals can be used, no additional benefits are usually obtained by exceeding such a concentration and the activity of the catalyst is generally reduced.

The supplemental metal(s) may be contained in the metal support and/or in the catalyst active phase on the surface of the support. Where it is desirable to include the supplemental metal(s) in an alloy-metal support, the supplemental metal(s) are preferably incorporated into the alloy at the time the alloy is formed. Where it is desirable to include the supplemental metal(s) in the catalyst active phase on the surface of the support, the supplemental metal may, in some instances, be deposited simultaneously with the copper. Where, however, the copper is deposited via displacement deposition or electroless plating (discussed above), the supplemental metal(s) are preferably added to the catalyst after the copper has been deposited because the supplemental metals tend to dissolve under displacement deposition conditions and to inhibit electroless plating. A supplemental metal(s) may typically be added to the catalyst surface by simply contacting the catalyst with an aqueous solution containing a salt (e.g., a sulfate, nitrate, chloride, etc.) of the supplemental metal(s).

C. Preferred Reaction Conditions

This dehydrogenation reaction is conducted in an alkaline environment (i.e., a basic environment). More specifically, this reaction is typically conducted in the presence of a strong base having a pK_(a) value of at least about 11, more preferably at least about 12, and even more preferably at least about 13. Suitable bases include, for example, alkali metal hydroxides (LiOH, NaOH, KOH, RbOH, or CsOH), alkaline-earth metal hydroxides (e.g., Mg(OH)₂ or Ca(OH)₂), NaH, and tetramethyl ammonium hydroxide. Of these bases, alkali metal hydroxides (particularly NaOH and KOH, and even more particularly NaOH) are often preferred because of their solubility in water under the reaction conditions, as well as their ready commercial availability and ease of handling.

The preferred amount of base introduced into the reaction zone depends on, for example, the moles of primary alcohol groups introduced into the reaction zone. Preferably, at least about one molar equivalent of base is introduced per mole of primary alcohol hydroxy groups. Thus, for example, if the base is NaOH and the primary alcohol is monoethanolamine, preferably at least about 1 mole of NaOH is introduced per mole of monoethanolamine. If, on the other hand, the primary alcohol is diethanolamine, preferably at least 2 moles of NaOH are introduced per mole of diethanolamine. In a particularly preferred embodiment, from about 1.05 to about 2.0 molar equivalents of base per alcohol hydroxyl group are introduced. The hydroxide may, for example, be in the form of flakes, powder, pellets, or an aqueous solution.

The reaction is normally conducted in a solvent in which the base is soluble. Preferably, a sufficient quantity of solvent is present in the reaction zone to dissolve essentially all (more preferably, all) the base. The solvent also preferably is present in a sufficient quantity to maintain the primary alcohol substrate and carboxylic acid salt product in a solubilized form. Water is normally the preferred solvent due to its low cost and ease of handling.

The preferred catalyst loading (i.e., the preferred amount of catalyst introduced into the reaction zone) depends on, for example, the amount of the primary alcohol substrate introduced into the reaction zone. Typically, the catalyst loading is at least about 1% by weight of the primary alcohol substrate (i.e., [mass of catalyst÷mass of primary alcohol substrate]×100%). More preferably, the catalyst loading is from about 1% to about 70% (still more preferably from about 10% to about 40%) by weight of the primary alcohol substrate.

The preferred catalyst loading also depends on, for example, the amount of total reaction mass. Typically, the catalyst loading is at least about 0.1% by weight of the total reaction mass (i.e., [mass of catalyst÷total reaction mass]×100%). More preferably, the catalyst loading is from about 0.1% to about 10% (even more preferably from about 3.5% to about 10%, and still even more preferably from about 3.5% to about 5%) by weight of the total reaction mass. Concentrations of greater than about 10 wt. % are difficult to filter. On the other hand, concentrations of less than about 0.1 wt. % tend to produce unacceptably low reaction rates.

It has been found that the catalysts of this invention typically are able to achieve a greater activity than the same volume of traditional copper-on-carbon catalysts (i.e., the catalysts of this invention typically have a greater activity per unit volume relative to the traditional copper-on-carbon catalysts). This greater activity per unit volume is advantageous because it often makes such catalysts easier to filter, thereby increasing throughput. Without being bound by any particular theory, Applicants believe that the greater activity per unit volume may be due, at least in part, to the catalysts of the present invention having a greater copper surface area relative to traditional copper-on-carbon catalysts.

The reaction typically is conducted at a temperature of at least about 70° C., preferably from about 120° to about 220° C., more preferably from about 140° to about 200° C., even more preferably from about 145° to about 155° C., and still even more preferably at about 150° C. (particularly when the primary alcohol is diethanolamine and the desired product is the salt of iminodiacetic acid). Although reaction temperatures outside of these ranges may be used, the results are typically less than optimal. For example, at temperatures of less than about 120° C., the reaction rate tends to be slow. And at temperatures greater than about 220° C., the catalyst normally begins to lose selectivity. To illustrate, as the reaction temperature exceeds about 150° C. (and particularly as the temperature exceeds about 220° C.), the dehydrogenation reaction of diethanolamine will tend to form more glycine salt byproduct, and, therefore, be less selective toward forming the desired iminodiacetic acid salt product.

The reaction is preferably conducted under pressure. More specifically, the reaction is normally conducted under a pressure which is sufficient to prevent boiling of the mixture at the reaction temperature. At reaction temperatures of from about 120° to about 220° C., the pressure preferably is at least about 5 kg/cm², more preferably from about 5 to about 30 kg/cm², even more preferably from about 5 to about 20 kg/cm², and most preferably from about 5 to about 11 kg/cm² (i.e., from about 75 to about 155 psig). Although greater pressures may be used, they are normally less desirable because pressures above about 30 kg/cm² tend to reduce the reaction rate.

The dehydrogenation reaction preferably is conducted under a non-oxidizing atmosphere (preferably, an atmosphere containing a noble gas and/or N₂, and more preferably N₂ when the reaction is conducted on a commercial level) to avoid oxidation of the catalyst surface (the atmosphere will also contain H₂ which evolves during the dehydrogenation). This preference stems from the fact that oxidization of the copper near the surface of the catalyst tends to reduce the activity and selectivity of the catalyst.

The dehydrogenation reaction may be carried out in a wide variety of batch, semi-batch, and continuous reactor systems. The configuration of the reactor is not critical. Suitable conventional reactor configurations include, for example, stirred-tank reactors, fixed bed reactors, trickle bed reactors, fluidized bed reactors, bubble flow reactors, plug flow reactors, and parallel flow reactors. Often, the more preferred reactor configurations are stirred-tank reactors. However, for when the hydrogen produced in the dehydrogenation reaction is fed to a fuel cell, the preferred reactor configuration comprises a fixed bed reactor followed by gas-liquid adsorption.

When the dehydrogenation is conducted in a continuous reactor system, the residence time in the reaction zone can vary widely depending on the specific catalyst and conditions employed. Likewise, when the dehydrogenation is conducted in a batch reactor, the reaction time typically will also vary widely depending on such factors. Normally, the dehydrogenation behaves as a first order reaction, particularly toward the end of the reaction. Thus, the preferred residence time in a continuous reaction zone (or the preferred reaction time in a batch reaction zone) will also depend on the desired degree of conversion.

D. Use of the Carboxylic Acid Salt Product to make N-(phosphonomethyl)glycine or a Salt Thereof.

Various carboxylic acid amine salts produced by this invention may be used as raw materials to prepare N-(phosphonomethyl)glycine and agronomically acceptable salts thereof in accordance with many well-known methods in the art. As used herein, an “agronomically acceptable salt” is defined as a salt which contains a cation(s) that allows agriculturally and economically useful herbicidal activity of an N-(phosphonomethyl)glycine anion. Such a cation may be, for example, an alkali metal cation (e.g., a K or Na ion), an ammonium ion, an isopropyl ammonium ion, a tetra-alkylammonium ion, a trialkyl sulfonium ion, a protonated primary amine, a protonated secondary amine, or a protonated tertiary amine.

Particularly preferable carboxylic acid amine salts that may be produced by this invention and used for making N-(phosphonomethyl)glycine compounds are salts of iminodiacetic acid (particularly alkali metal salts of iminodiacetic acid). These carboxylic acid salts may be phosphonomethylated in a reaction zone containing HCl, phosphorous acid (H₃PO₃), and formaldehyde (CH₂O) to form N-(phosphonomethyl)iminodiacetic acid. See, e.g., Gentilcore, U.S. Pat. No. 4,775,498 (also reporting that the HCl and H₃PO₃ may optionally be formed by adding PCl₃ to water). The N-(phosphonomethyl)iminodiacetic acid may, in turn, be contacted with oxygen in the presence of a catalyst to oxidatively cleave a carboxymethyl group to form N-(phosphonomethyl)glycine. Many catalysts are known in the art for conducting this oxidation, and include, for example, carbon catalysts (see, e.g., Hershman, U.S. Pat. No. 3,969,398; and Chou, U.S. Pat. Nos. 4,624,937 and 4,696,772); a carbon catalyst along with a noble metal co-catalyst supported on aluminosilicate (see, e.g., Felthouse, U.S. Pat. No. 4,582,650), and catalysts comprising a noble metal supported on carbon (see, e.g., Franz, U.S. Pat. No. 3,950,402; Ramon et al., U.S. Pat. No. 5,179,228; and Ebner et al., PCT/US99/03402).

Alternatively, for example, a salt of glycine (particularly an alkali metal salt of glycine) may be converted to N-(phosphonomethyl)glycine by a wide variety of methods well-known in the art. Many such methods are summarized in Franz, et al., Glyphosate: A Unique Global Herbicide (ACS Monograph 189, 1997) at pp. 234-39.

As a further example, a salt of an N-substituted glycine (e.g., a salt of N-(methyl)glycine, also known as “sarcosine”) may be phosphonomethylated by, for example, reacting it with PCl₃ in water, and then filtering out the resulting salt and adding CH₂O. The resulting product is an N-substituted-N-(phosphonomethyl)glycine (e.g., N-methyl-N-(phosphonomethyl)glycine). A solution containing the N-substituted-N-(phosphonomethyl)glycine may then be contacted with oxygen in the presence of a noble metal catalyst (preferably platinum) to form N-(phosphonomethyl)glycine. See Morgenstern et al., U.S. Pat. No. 6,005,140. Other approaches for making N-(phosphonomethyl)glycine from N-substituted glycine compounds include, for example, phosphonomethylating N-benzylglycine to form N-benzyl N-(phosphonomethyl)glycine, and then (a) reacting the N-benzyl N-(phosphonomethyl)glycine with hydrobromic or hydroiodic acid to cleave the benzyl group (see, e.g., Parry et al., U.S. Pat. No. 3,956,370), or (b) converting the N-benzyl N-(phosphonomethyl)glycine to N-(phosphonomethyl)glycine via hydrogenolysis (see, e.g., European Patent Application No. 55,695; and Maier, L., Phosphorus, Sulfur and Silicon, 61, 65-7 (1991)); and phosphonomethylating-t-butylglycine to form N-t-butyl N-(phosphonomethyl)glycine, and then converting the N-t-butyl N-(phosphonomethyl)glycine to N-(phosphonomethyl)glycine via acid hydrolysis (see Gaertner, U.S. Pat. No. 3,927,080).

EXAMPLES

The following examples merely further illustrate and explain Applicants' invention. Applicants' invention should not be considered to be limited to any of the details in these examples.

The disclosure of Examples 1 through 20 at Col. 19, line 57 to Col. 28, line 44 of U.S. Pat. No. 6,376,708 is hereby incorporated herein by reference.

Example 21 Preparation of a Copper-Coated, Copper-Doped Nickel Sponge

This example demonstrates the electrochemical displacement deposition of copper onto a copper-doped nickel sponge catalyst under basic conditions followed by electrochemical displacement deposition of copper under acidic conditions.

A copper-doped nickel sponge catalyst (8.96 g), having an initial composition of 78.4% Ni, 8.3% Cu and 13.2% Al (from W.R. Grace & Co.) was slurried into nitrogen-sparged water (300 ml). A solution of 12% NaBH₄ in 14M NaOH was added to the slurry for the removal of surface oxidation. The suspension was stirred for 15 minutes with nitrogen sparging and the catalyst was allowed to settle. The supernatant was decanted and the catalyst was again slurried into nitrogen-sparged water (200 ml).

Electrochemical displacement deposition under basic conditions was begun by adjusting the pH of the catalyst slurry to approximately 7 by the addition of acetic acid. A solution of CuSO₄.5H₂O (8.80 g, equivalent to 25 wt % Cu with respect to the catalyst), tetrasodium EDTA dihydrate (17.60 g) and water (150 ml) was added to the catalyst slurry. To this mixture, a solution of 2.5N NaOH (56 ml or 4.0 equivalents) in water (50 ml) was added dropwise with continuous stirring and nitrogen sparging. The pH rose from 9.3 to 12.4. A nearly clear supernatant was then decanted.

Immediately after decantation of the previous plating solution, a mixture of 50% gluconic acid (27.6 g or 2.0 equivalents), 2.5N NaOH (5.6 ml or 0.4 equivalents) and water (400 ml) was heated in a 95° C. oil bath and added to the catalyst. A copper salt solution containing CuSO₄.5H₂O (8.80 g) dissolved in water (100 ml) was added to the catalyst suspension dropwise over 30 minutes with continuous stirring and nitrogen sparging. During the copper salt addition, the catalyst suspension cooled from 67° C. to 30° C. and the pH of the suspension fell from 3.3 to 2.6. A blue-green supernatant was then decanted and the catalyst was solvent exchanged with nitrogen-sparged 50% NaOH for transfer to a dehydrogenation reactor.

Example 22 Use of Catalyst of Example 21 to Dehydrogenate Diethanolamine to Form Disodium Iminodiacetic Acid

This example demonstrates the use of the catalyst prepared in Example 21 to dehydrogenate diethanolamine to form disodium iminodiacetic acid.

Dehydrogenation of diethanolamine was conducted in a 300 ml autoclave reactor constructed of Hastelloy C (high strength nickel-based alloy) and equipped with a back pressure regulator, H₂ mass flow meters, and a charge pot which allowed reagents and rinse water to be added to the reactor under inert gas. The reactor was first flushed with argon (when conducting this reaction on a commercial scale, N₂ would be preferred). Afterward, the entire amount of the catalyst prepared in Example 21 was suspended in an aqueous solution containing 50 wt. % NaOH (61.5 g). This suspension was sparged with N₂, and introduced into the reactor, along with N₂-sparged deionized water (40 ml) and a N₂-sparged aqueous solution containing 78.95% diethanolamine (47.5 g). The reactor was then sealed and flushed with N₂.

The reaction was run for 11 reaction cycles as shown in Table 13. During each reaction cycle, the mixture was continuously stirred, and the temperature and pressure were maintained substantially constant. At the endpoint of each reaction cycle, the reactor was cooled, and N₂-sparged deionized water (80 ml) was added to the reactor. The liquid in the reactor was then drained and collected as product. Afterward, the catalyst was rinsed twice more with N₂-sparged deionized water (80 ml portions). This rinse water was also collected as product. The catalyst was then subjected to the additional reaction cycles by introducing the same quantities of N₂-sparged diethanolamine, NaOH, and water into the reactor and conducting the reaction and product recovery in the same manner as the first cycle.

After performing the 11-reaction series described above and in Table 13, the catalyst had an overall composition of 57.6% Ni, 36.3% Cu and 6.1% Al. TABLE 13 Performance of the catalyst of Example 21 in the dehydrogenation of diethanolamine Temp P End- Glycine IDA Cycle (° C.) (psi) point Time (%) (%) 1 150 135 8 sccm 1:51 1.76 93.4 2 150 135 8 sccm 2:28 2.27 92.3 3 150 135 8 sccm 2:44 2.27 92.1 4 150 135 8 sccm 2:58 2.18 90.9 5 150 135 15 sccm  2:56 1.88 91.2 6 145 135 8 sccm 3:46 1.80 93.1 7 A 135 8 sccm 4:00 1.61 92.3 8 150 100 abort — — — 9 150 100 8 sccm 3:15 1.93 95.2 10 150 100 8 sccm 3:02 1.74 95.8 11 145 100 8 sccm 4:00 1.64 95.7 A = 145° C. initial temperature, raised to 150° C. midway through the run

Example 23 Electroless Plating of Nickel Sponge with Copper in a Non-Aqueous Solvent

This example demonstrates the electroless plating of copper onto a nickel sponge catalyst using a non-aqueous solvent.

Nickel sponge (15 g) was de-watered by sequentially washing and decanting with a 5% aqueous solution of sodium gluconate, THF and toluene. The catalyst was then slurried into a solution containing 10% Cu ion as Cullneodecanoate in toluene (24.8 g), ethylene diamine (1.76 g) and toluene (21 ml).

The catalyst slurry was then charged to a hydrogenation reactor. The reactor gas cap was purged with N₂ and H₂. The electroless plating was begun by stirring the slurry under 25 to 45 psig of H₂ for 3 hours while linearly ramping the temperature inside the reactor from 25° C. to 80° C. The H₂ consumed during the reaction was replaced to maintain pressure in the reactor.

After the reaction was complete, the reactor was cooled to room temperature and the gas cap was purged with N₂. The supernatant, which had a light tan color, was decanted. The catalyst was then slurried into another copper ion solution identical to that described above and the plating procedure was repeated.

After the second electroless plating run, the reactor was cooled, the gas cap was purged with N₂ and the supernatant, which again had a light tan color, was decanted. The catalyst was then washed sequentially with toluene, THF, 1% aqueous NaOH and water.

Example 24 Use of Catalyst of Example 23 to Dehydrogenate Diethanolamine to Form Disodium Iminodiacetic Acid

Dehydrogenation of diethanolamine was conducted using the catalyst of Example 23. The dehydrogenation was conducted in a 300 ml autoclave reactor constructed of Hastelloy C (high strength nickel-based alloy) and equipped with a back pressure regulator, H₂ mass flow meters, and a charge pot which allowed reagents and rinse water to be added to the reactor under inert gas. The reactor was first flushed with argon (when conducting this reaction on a commercial scale, N₂ would be preferred). Afterward, the entire amount of the catalyst prepared in Example 23 was suspended in an aqueous solution containing 50 wt. % NaOH (61.5 g). This suspension was sparged with N₂, and introduced into the reactor, along with N₂-sparged deionized water (40 ml) and a N₂-sparged aqueous solution containing 78.95% diethanolamine (47.5 g). The reactor was then sealed and flushed with N₂.

During the reaction, the mixture was continuously stirred, the pressure was maintained at 135 psig using the back pressure regulator, and the temperature was maintained at 150° C. When the H₂ generation from the reaction decreased to 5 sccm, the reactor was cooled, and N₂-sparged deionized water (80 ml) was added to the reactor. The liquid in the reactor was then drained and collected as product. Afterward, the catalyst was rinsed twice more with N₂-sparged deionized water (80 ml portions). This rinse water was also collected as product. Subsequently, a second dehydrogenation was conducted by introducing the same quantities of N₂-sparged diethanolamine, NaOH, and water into the reactor and conducting the reaction and product recovery in the same manner as the first cycle.

The products of both cycles were analyzed using high pressure liquid chromatography (“HPLC”). The results are shown in Table 14. TABLE 14 Performance of the Catalyst Prepared in Example 23 in Diethanolamine Dehydrogenation Disodium Sodium Iminodiacetic Glycine Cycle No. Cycle Time (hr) Acid Yield Yield 1 3.3 85.4% 2.67% 2 4.5 87.2% 2.99%

Example 25 Preparation of a Copper-Doped Nickel Sponge Catalyst

This example describes the preparation of a Cu-doped Ni sponge catalyst that was supplied by the Davison Division of W.R. Grace and Co., Chattanooga, Tenn. The method of preparation was provided to the assignee hereof for use in describing the catalyst. As further explained herein, this catalyst is useful without further modification in catalyzing the dehydrogenation of a primary alcohol such as diethanolamine. Advantageously, it may also be plated with Cu to produce a modified catalyst having a Cu-containing active phase that is also useful in catalyzing such reactions.

Powdered aluminum, nickel and copper were mixed to provide a mixture containing 50% by weight Al, 45% by weight Ni and 5% by weight Cu. The mixture was placed in a graphite crucible/mold and heated in a furnace under an argon atmosphere to form an alloy. The furnace reached a maximum temperature of 1600° C. over a period of 4 hours and this peak temperature was maintained for an additional 15 minutes. The resulting alloy was then cooled to room temperature under Ar over a 3-hour period.

The alloy was then crushed and ground to powder, and sieved using a 270 mesh U.S. Std. sieve. The powder passing through the 270 mesh sieve was then subsequently activated.

The catalyst activation comprised gradually adding, with stirring, the alloy powder to a vessel containing a 30% by weight solution of NaOH in water. The ratio of alloy powder to NaOH solution was 0.22:1 on a weight basis. The alloy was added to the solution and then digested (further stirred and heated) for a total period of 4 hours and 15 minutes. The temperature of the solution during alloy addition and digestion ranged from about 95° to about 105° C.

After digestion, the catalyst was washed with water by a decant method until the pH of the slurry reached 9. The resulting catalyst had a weight basis composition of 77.0% Ni, 8.9% Cu and 13.8% Al. The average particle size was 23 microns as determined by Malvern light scattering method after 30 seconds ultrasound dispersion.

The above process was repeated using an initial metal mixture of 50% by weight Al, 43% by weight Ni and 7% Cu. The resulting copper-doped nickel sponge had a weight basis composition of 69.5% Ni, 11.2% Cu and 18.9% Al.

Example 26 Preparation of a Zinc-Doped Copper Alloy Sponge Catalyst

This example describes the preparation of a Zn-doped copper alloy sponge catalyst that was supplied by the Davison Division of W.R. Grace and Co. The method of preparation was provided to the assignee hereof for use in describing the catalyst. As further explained herein, this catalyst is useful without further modification in catalyzing the dehydrogenation of a primary alcohol such as diethanolamine. Advantageously, it may also be plated with Cu to produce a modified catalyst having a Cu-containing active phase that is also useful in catalyzing such reactions.

Powdered aluminum, nickel, zinc and copper were mixed to provide a mixture containing 50% by weight Al, 42.5% by weight Ni, 2.5% by weight Zn and 5% by weight Cu. The mixture was placed in a graphite crucible/mold and heated in a furnace under an argon atmosphere to form an alloy. The furnace reached a maximum temperature of 1000° C. over a period of 4 hours and this peak temperature was maintained for an additional 15 minutes. The resulting alloy was then cooled to room temperature under Ar over a 3-hour period.

The alloy was then crushed and ground to powder, and sieved using a 270 mesh U.S. Std. sieve. The powder passing through the 270 mesh sieve was then subsequently activated.

The catalyst activation comprised gradually adding, with stirring, the alloy powder to a vessel containing a 35% by weight solution of NaOH in water. The ratio of alloy powder to NaOH solution was 0.26:1 on a weight basis. The alloy was added; to the solution and then digested (further stirred and heated) for a total period of 4 hours and 45 minutes. The temperature of the solution during alloy addition and digestion ranged from about 95° to about 110° C.

After digestion, the catalyst was washed with water by a decant method until the pH of the slurry reached 9. The resulting catalyst had a weight basis composition of 81.4% Ni, 6.3% Cu, 11.5% Al and 0.4% Zn. The average particle size was 24 microns as determined by Malvern light scattering method after 30 seconds ultrasound dispersion.

Example 27 Preparation of a Copper-Plated Nickel Sponge Catalyst

This example demonstrates the electrochemical displacement deposition of copper onto a nickel sponge catalyst.

A nickel sponge catalyst (9.0 g), Raney® nickel 4200 from W.R. Grace & Co., Davison Division, Chattanooga, Tenn., was weighed out (assuming a density factor of 1.16) and added to a warm (about 40°-60° C.) nitrogen-sparged mixture of 50% gluconic acid (4 g), gluconic acid (0.5 g) and water (300 ml). The mixture was stirred for 15 minutes to remove surface oxides. Acetone (100 ml) was added to the mixture, which was stirred for another 20 minutes.

The supernatant was decanted from the catalyst and replaced with a nitrogen-sparged solution of CuSO₄.5H₂O (7.0 g) and tetrasodium EDTA dihydrate (14.0 g) in water (300 ml). 2.5 N NaOH (45 ml, 2 equivalents with respect to copper sulfate) was added to the catalyst suspension dropwise over 30 minutes with continuous stirring and nitrogen sparging.

The supernatant was again decanted and replaced with a nitrogen-sparged mixture of 50% gluconic acid (17 g) and ethylene diamine (1.7 g, 0.33 equivalents with respect to gluconic acid) in water (300 ml). A solution of copper sulfate pentahydrate (4.2 g) in water (100 ml) was then added to the catalyst suspension dropwise over 25 minutes with continuous stirring and nitrogen sparging.

The supernatant was decanted and replaced with a nitrogen-sparged solution of copper sulfate pentahydrate (3.5 g) and tetrasodium EDTA dihydrate (7.0 g) in water (300 ml). 2.5N NaOH (23 ml) was added over a period of 8 minutes. The supernatant was decanted and the catalyst was rinsed with water (500 ml) before use in the diethanolamine dehydrogenation reaction described below in Example 29.

Example 28 Preparation of a Copper-plated, Iron-Modified Nickel Sponge Catalyst

This example demonstrates the electrochemical displacement deposition of copper simultaneously with the iron modification of a nickel sponge catalyst.

A nickel sponge catalyst (9.0 g), Raney® 4200 from W.R. Grace & Co., Davison Division, Chattanooga, Tenn., was weighed out (assuming a density factor of 1.16) and added to a warn (about 40⁰-60° C.) nitrogen-sparged mixture of 50% gluconic acid (4 g), gluconic acid (0.5 g) and water (300 ml). The mixture was stirred for 15 minutes to remove surface oxides. Acetone (100 ml) was added to the mixture, which was stirred for another 30 minutes.

The supernatant was decanted from the catalyst and replaced with a nitrogen-sparged solution of CuSO₄.5H₂O (7.0 g) and tetrasodium EDTA dihydrate (14.0 g) in water (300 ml). 2.5 N NaOH (45 ml, 2 equivalents with respect to copper sulfate) was added to the catalyst suspension dropwise over 30 minutes with continuous stirring and nitrogen sparging. Then FeSO₄.7H₂O (1.18 g) was added dropwise over a period of 45 minutes with continuous stirring and nitrogen sparging.

The supernatant was again decanted and replaced with a nitrogen-sparged mixture of 50% gluconic acid (17 g) and ethylene diamine (1.7 g, 0.33 equivalents with respect to gluconic acid) in water (300 ml). A solution of CuSO₄.5H₂O (4.2 g) in water (100 ml) was then added to the catalyst suspension dropwise over 25 minutes with continuous stirring and nitrogen sparging. Then FeSO₄.7H₂O (1.18 g) was added dropwise over a period of 37 minutes with continuous stirring and nitrogen sparging.

The supernatant was decanted and replaced with a nitrogen-sparged solution of CuSO₄.5H₂O (3.5 g) and tetrasodium EDTA dihydrate (7.0 g) in water (300 ml). 2.5N NaOH (23 ml) was added over a period of 8 minutes. Then FeSO₄ 7H₂O (1.18 g) was added to the catalyst suspension dropwise over a period of 17 minutes with continuous stirring and nitrogen sparging. The supernatant was decanted and the catalyst was rinsed with water (500 ml) before use in the diethanolamine dehydrogenation reaction described below in Example 29.

Example 29 Comparison of the Catalysts Prepared in Examples 27 and 28 in Dehydrogenating Diethanolamine to Form Disodium Iminodiacetic Acid

This example compares the performance of the catalysts prepared in Examples 27 and 28 for the dehydrogenation of diethanolamine to form disodium iminodiacetic acid. The dehydrogenation reactions were conducted using the reaction conditions described in Example 24 over five reaction cycles with 6% catalyst loading. Generally, the catalyst of Example 28 incorporating iron as a catalyst modifier achieved significantly lower glycine and sarcosine levels than the catalyst of Example 27 without iron as a catalyst modifier. The results are shown in Tables 15 and 16 below. TABLE 15 Dehydrogenation Results using the Catalyst of Example 27 Cycle Glycine Yield Sarcosine Yield DSIDA Yield No. Cycle Time (mole %) (mole %) (mole %) 1 1 hour, 54 2.69 6.2 87.0 minutes 2 2 hours, 25 2.99 8.0 85.1 minutes 3 2 hours, 45 3.15 8.3 83.0 minutes 4 2 hours, 40 3.02 6.7 84.0 minutes 5 2 hours, 51 2.98 6.9 86.4 minutes

TABLE 16 Dehydrogenation Results using the Catalyst of Example 28 Cycle Glycine Yield Sarcosine Yield DSIDA Yield No. Cycle Time (mole %) (mole %) (mole %) 1 2 hours, 10 2.63 5.9 83.0 minutes 2 2 hours, 36 3.21 6.7 85.5 minutes 3 2 hours, 40 2.72 5.9 86.2 minutes 4 2 hours, 35 2.63 5.0 86.1 minutes 5 2 hours, 42 2.59 4.4 78.8 minutes

The above description of the preferred embodiments is intended only to acquaint others skilled in the art with the invention, its principles, and its practical application, so that others skilled in the art may adapt and apply the invention in its numerous forms, as may be best suited to the requirements of a particular use. The present invention, therefore, is not limited to the above embodiments, and may be variously modified.

With reference to the use of the word(s) “comprise” or “comprises” or “comprising” in this specification (including the claims), Applicants note that unless the context requires otherwise, those words are used on the basis and clear understanding that they are to be interpreted inclusively, rather than exclusively, and that Applicants intend each of those words to be so interpreted in construing this specification (including the claims).

The entire texts of all U.S. patents and other references cited herein are hereby incorporated by reference into this patent. 

1. A process for the preparation of a carboxylic acid salt by the dehydrogenation of a primary alcohol, the process comprising: contacting an alkaline mixture comprising said primary alcohol with a dehydrogenation catalyst, said catalyst comprising a copper-containing active phase at the surface thereof, iron as a catalyst modifier and a supporting structure comprising nickel.
 2. A process as set forth in claim 1 wherein the active phase at the surface of said catalyst comprises at least about 50% by weight copper.
 3. A process as set forth in claim 1 wherein said catalyst comprises from about 0.002% to about 5% by weight iron as a catalyst modifier.
 4. A process as set forth in claim 3 wherein said catalyst comprises from about 0.05 to about 3% by weight iron as a catalyst modifier.
 5. A process as set forth in claim 3 wherein said catalyst comprises from about 0.5 to about 1.5% by weight iron as a catalyst modifier.
 6. A process as set forth in claim 1 wherein said supporting structure comprises at least about 10% by weight nickel.
 7. A process as set forth in claim 6 wherein said catalyst comprises a surface stratum comprising said active phase and said iron catalyst modifier, said surface stratum containing from about 0.005 to about 0.5 grams of copper per gram of said supporting structure.
 8. A process as set forth in claim 6 wherein said catalyst comprises from about 0.002% to about 5% by weight iron at the surface thereof as a catalyst modifier.
 9. A process as set forth in claim 6 wherein said catalyst comprises from about 0.05 to about 3% by weight iron at the surface thereof as a catalyst modifier.
 10. A process as set forth in claim 6 wherein said catalyst comprises from about 0.5 to about 1.5% by weight iron at the surface thereof as a catalyst modifier.
 11. A process as set forth in claim 6 wherein the supporting structure comprises a metal sponge and the surface active phase comprises a copper-containing outer stratum deposited on the metal sponge.
 12. A process as set forth in claim 11 wherein the iron catalyst modifier is deposited on the metal sponge supporting structure as an outer stratum.
 13. A process as set forth in claim 6 wherein the catalyst comprises a particulate catalyst, the particles of which have a yield strength of at least about 100 MPa.
 14. A process as set forth in claim 1, wherein said primary alcohol comprises a compound corresponding to the formula:

wherein n is an integer ranging from 2 to 20; and R¹ and R² are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl.
 15. A process as set forth in claim 14, wherein R¹ and R² are independently hydrogen; —(CH₂)_(x)—(CH₃)_(m), x being an integer ranging from 0 to about 19, m being either 1 or 2; —(CH₂)_(y)—OH, y being an integer ranging from 1 to about 20; (CH₂)_(n)—COOH, z being an integer ranging from 1 to about 19; or phosphonomethyl.
 16. A process as set forth in claim 15, wherein n is 2; R¹ is hydrogen; and R² is hydrogen, hydrocarbyl, or substituted hydrocarbyl.
 17. A process as set forth in claim 16, wherein R² is hydrocarbyl.
 18. A process as set forth in claim 17, wherein R² is —(CH₂)_(x)—(CH₃)_(m).
 19. A process as set forth in claim 18, wherein R² is —CH₃.
 20. A process as set forth in claim 14, wherein said primary alcohol is selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine.
 21. A process as set forth in claim 14, wherein said carboxylic acid salt comprises an alkali metal salt of iminodiacetic acid, glycine, or an N-alkyl-glycine.
 22. A process as set forth in claim 14, wherein said process further comprises phosphonomethylating said carboxylic acid salt to form N-(phosphonomethyl) iminodiacetic acid or a salt thereof.
 23. A process as set forth in claim 22, wherein said process further comprises oxidizing said N-(phosphonomethyl)iminodiacetic acid to N-(phosphonomethyl) glycine or a salt thereof.
 24. A process as set forth in claim 1, wherein the process further comprises collecting the hydrogen produced by the dehydrogenation reaction and transferring said hydrogen to a fuel cell for the production of electric power.
 25. A process as set forth in claim 1 wherein the supporting structure comprises a metal sponge support comprising at least about 10% by weight nickel and from about 2% to about 30% by weight copper.
 26. A process as set forth in claim 25 wherein said catalyst comprises a surface stratum comprising said copper-containing active phase and said iron catalyst modifier, said surface stratum containing from about 0.005 to about 0.5 grams of copper per gram of said supporting structure.
 27. A process as set forth in claim 25 wherein said iron catalyst modifier comprises from about 0.002% to about 5% by weight of the catalyst.
 28. A process as set forth in claim 25 wherein said iron catalyst modifier comprises from about 0.05 to about 3% by weight of the catalyst.
 29. A process as set forth in claim 25 wherein said iron catalyst modifier comprises from about 0.5 to about 1.5% by weight of the catalyst.
 30. A process as set forth in claim 25 wherein the copper-containing active phase and the iron catalyst modifier comprise an outer stratum deposited on the metal sponge supporting structure.
 31. A process as set forth in claim 30 wherein said outer stratum is deposited by a method comprising electrochemical displacement reaction between a metal of said supporting structure and copper ions.
 32. A process as set forth in claim 30 wherein said outer stratum is deposited by a method comprising electroless plating of copper metal on said metal sponge support.
 33. A process as set forth in claim 25, wherein said primary alcohol comprises a compound corresponding to the formula:

wherein n is an integer ranging from 2 to 20; and R¹ and R² are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl.
 34. A process as set forth in claim 25, wherein said primary alcohol is selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine.
 35. A process as set forth in claim 25, wherein said carboxylic acid salt comprises an alkali metal salt of iminodiacetic acid, glycine, or an N-alkyl-glycine.
 36. A process as set forth in claim 25, wherein said process further comprises phosphonomethylating said carboxylic acid salt to form N-(phosphonomethyl) iminodiacetic acid or a salt thereof.
 37. A process as set forth in claim 36, wherein said process further comprises oxidizing said N-(phosphonomethyl)iminodiacetic acid to N-(phosphonomethyl) glycine or a salt thereof.
 38. A process as set forth in claim 25, wherein the process further comprises collecting the hydrogen produced by the dehydrogenation reaction and transferring said hydrogen to a fuel cell for the production of electric power.
 39. A process as set forth in claim 1, wherein said supporting structure comprises a metal sponge comprising at least about 50% by weight nickel.
 40. A process as set forth in claim 1 wherein said catalyst has a heterogeneous structure comprising the supporting structure, a surface active phase and iron as a catalyst modifier, wherein: the supporting structure comprises at least about 10% by weight nickel, the surface active phase contains at least about 50% by weight copper, and the iron catalyst modifier comprises from about 0.002% to about 5% by weight of the catalyst.
 41. A process for the preparation of a carboxylic acid salt by the dehydrogenation of a primary alcohol, the process comprising: introducing a primary alcohol, a base, and a dehydrogenation catalyst into a reaction zone to form a dehydrogenation reaction mixture; and introducing a source of iron into said dehydrogenation reaction mixture as a catalyst modifier.
 42. A process as set forth in claim 41 wherein said dehydrogenation catalyst comprises a copper-containing active phase at the surface of a supporting structure and said supporting structure comprises a metal and contains at least about 10% by weight nickel.
 43. A process as set forth in claim 42, wherein the active phase at the surface of the supporting structure comprises at least about 50% by weight copper.
 44. A process as set forth in claim 42 wherein the supporting structure comprises a metal sponge.
 45. A process as set forth in claim 44 wherein said metal sponge supporting structure comprises at least about 10% by weight nickel and from about 2 to about 30% by weight copper.
 46. A process as set forth in claim 41 wherein the source of said iron is selected from the group consisting of Na₂(FeO₄) in concentrated sodium hydroxide, powders of iron and carbon steel, and powders of iron oxides.
 47. A process as set forth in claim 41 wherein said primary alcohol comprises a compound corresponding to the formula:

wherein n is an integer ranging from 2 to 20; and R¹ and R² are independently hydrogen, hydrocarbyl, or substituted hydrocarbyl.
 48. A process as set forth in claim 41, wherein said primary alcohol is selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine.
 49. A process as set forth in claim 41, wherein said carboxylic acid salt comprises an alkali metal salt of iminodiacetic acid, glycine, or an N-alkyl-glycine.
 50. A process as set forth in claim 41, wherein said process further comprises phosphonomethylating said carboxylic acid salt to form N-(phosphonomethyl) iminodiacetic acid or a salt thereof.
 51. A process as set forth in claim 50, wherein said process further comprises oxidizing said N-(phosphonomethyl)iminodiacetic acid to N-(phosphonomethyl) glycine or a salt thereof.
 52. A process as set forth in claim 41, wherein the process further comprises collecting the hydrogen produced by the dehydrogenation reaction and transferring said hydrogen to a fuel cell for the production of electric power.
 53. A catalyst composition comprising a supporting structure having a copper-containing active phase and iron as a catalyst modifier at the surface thereof, said supporting structure comprising a metal and containing at least about 10% by weight nickel.
 54. A catalyst composition as set forth in claim 53 wherein the active phase at; the surface of said catalyst comprises at least about 50% by weight copper.
 55. A catalyst composition as set forth in claim 53 wherein said iron catalyst modifier comprises from about 0.002% to about 5% by weight of the catalyst.
 56. A catalyst composition as set forth in claim 53 wherein said iron catalyst modifier comprises from about 0.05 to about 3% by weight of the catalyst.
 57. A catalyst composition as set forth in claim 53 wherein said iron catalyst modifier comprises from about 0.5 to about 1.5% by weight of the catalyst.
 58. A catalyst composition as set forth in claim 53 wherein said supporting structure comprises a metal sponge comprising at least about 10% by weight nickel and from about 2% to about 30% by weight copper.
 59. A catalyst composition as set forth in claim 58, wherein said metal sponge supporting structure comprises at least about 50% by weight nickel.
 60. A catalyst composition as set forth in claim 53 wherein said catalyst has a heterogeneous structure comprising the supporting structure, the surface active phase and the iron catalyst modifier wherein: the supporting structure comprises a metal comprising at least about 10% by weight nickel; the surface active phase comprises at least about 50% by weight copper; and the iron catalyst modifier comprises from about 0.002% to about 5% by weight of the catalyst.
 61. A catalyst composition as set forth in claim 53 wherein said catalyst comprises a surface stratum comprising said active phase and said iron catalyst modifier, said surface stratum containing between about 0.005 and about 0.5 grams of copper per gram of said supporting structure.
 62. A catalyst composition as set forth in claim 53 wherein the supporting structure comprises a metal sponge wherein the surface active phase and iron catalyst modifier comprise an outer stratum deposited on the metal sponge.
 63. A catalyst composition as set forth in claim 62 wherein said outer stratum is deposited by a method comprising electrochemical displacement reaction between a metal of said support and copper ions.
 64. A catalyst composition as set forth in claim 62 wherein said outer stratum is deposited by a method comprising electroless plating of copper metal on said metal sponge supporting structure.
 65. A catalyst composition as set forth in claim 53 wherein said catalyst comprises a particulate catalyst.
 66. A catalyst composition as set forth in claim 53 wherein said supporting structure comprises a metal sponge and said catalyst is characterized as being produced by a process comprising depositing a copper-containing active phase and an iron catalyst modifier on the surface of a metal sponge supporting structure containing at least about 60% by weight nickel and from about 2% to about 30% by weight copper.
 67. A catalyst composition as set forth in claim 66, wherein said copper-containing active phase and said iron catalyst modifier are deposited onto the surface of said metal sponge supporting structure by a method comprising an electrochemical displacement reaction of the metal of the supporting structure with copper and iron ions.
 68. A process for making an oxidation catalyst, the process comprising depositing a copper-containing active phase and an iron catalyst modifier onto the surface of a supporting structure comprising a metal and containing at least about 10% nickel and from about 2% to about 30% copper.
 69. A process as set forth in claim 68, wherein said process further comprises contacting said metal supporting structure with a reducing agent before depositing said copper-containing active phase.
 70. A process as set forth in claim 68, wherein said copper-containing active phase is deposited onto the surface of said metal supporting structure by a method comprising an electrochemical displacement reaction of the metal of the supporting structure with copper ions before the deposition of iron onto the surface of the catalyst.
 71. A process as set forth in claim 68, wherein said copper-containing active phase is deposited onto the surface of said metal supporting structure by a method comprising electroless plating before the deposition of iron onto the surface of the catalyst. 